ES2510548T3 - Hyperbranched Polyesters - Google Patents

Abstract

Hyperbranched polyesters with a weight average molecular weight Mw of between 500 and 300,000 g / mol, obtainable by conversion of at least one oligohydroxycarboxylic acid in the presence of at least one catalyst and in the presence of at least one inert solvent under the reaction conditions, characterized in that the temperature during the reaction is adjusted to no more than 120 ° C, the average functionality of carboxy functions per molecule amounts to more than 0.8 and less than 1.05 and the average functionality of ether groups -CH2-O- CH2- amounts to less than 0.20 and the catalyst is selected from the group consisting of acids, metal chelates, metal alcoholates, metal alkanoates and organometallic compounds.

Description

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DESCRIPTION

Hyperbranched Polyesters

The present invention relates to new hyperbranched polyesters based on oligohydroxycarboxylic acids with defined functionality.

Hyperbranched polyesters based on dimethylolpropionic acid are known, for example, from EP 630389 B1, WO 00/222700 or EP 1582548 A.

However, in these hyperbranched polyesters it is disadvantageous that they are prepared under relatively indeterminate reaction conditions, such that they have irregular functionalities.

Also perfectly dendrimeric polyesters containing dimethylolpropionic acid units are known, for example, by E. Malmström et al., Macromolecules 2004, 37 (2), 322-329.

In these compounds it is disadvantageous that in the synthesis dimethylolpropionic acid cannot be used, but, to achieve the high selectivities, dimethylolpropionic acid provided with an acetonide as a protecting group.

Therefore, such a synthesis requires, on the one hand, non-economical acetonide-protected dimethylolpropionic acid as a starting component and, on the other hand, reaction steps for the removal of these protecting groups.

This document also describes the need for hyperbranched polyesters containing groups that can be introduced by polymerization such as, for example, acrylate or methacrylate groups to use them, for example, in the preparation of polymers. In this regard it is important that such compounds have exactly one radical polymerizable group, since compounds with two or more radical polymerizable groups would lead to crosslinking of the polymers.

Therefore, there is a need for hyper-branched hyper-synthesized polyesters that are, in essence, monofunctional in relation to radical polymerizable groups.

The objective of the present invention was to provide hyperbranched polyesters with a regular structure that could be prepared starting from simple synthetic constituent elements without the need for protective group operations that were, in essence, monofunctional in relation to carboxy groups and that could easily be converted into also essentially monofunctional compounds, for example, polymerizable by radicals.

The objective has been achieved by hyperbranched polyesters with a weight average molecular weight Mw between 500 and 300,000 g / mol, obtainable by conversion of at least one oligohydroxycarboxylic acid, in the presence of at least one catalyst selected from the group consisting of acids, chelates of metal, metal alcoholates, metal alkanoates and organometallic compounds; and in the presence of at least one inert solvent under the reaction conditions, characterized in that the temperature during the reaction is adjusted to no more than 120 ° C, the average functionality of carboxy functions per molecule amounts to more than 0.8 and less than 1 , 05 and the average functionality of ether groups -CH2-O-CH2- amounts to less than 0.20.

Within the framework of the present invention, hyperbranched polyesters means macromolecules not cross-linked with hydroxy and carboxy groups that are both structurally and molecularly irregular. On the one hand, starting from a central molecule they can be structured analogously to dendrimers, however, with irregular chain length of the branches. On the other hand, they can also be linearly structured with branched functional side groups or, however, as a combination of the two ends, have linear and branched parts of the molecule. For the definition of dendrimeric and hyperbranched polymers see also P.

J. Flory, J. Am. Chem. Soc., 1952, 74, 2718 and H. Frey et al., Chem. Eur. J., 2000, 6 (14), 2499.

By "highly branched" and "hyperbranched" is understood, in the context of the present invention, that the degree of branching (Degree of Branching, DB), that is, the average amount of dendritic bonds plus the average number of groups terminals per molecule, divided by the sum of the average amount of dendritic bonds, the average amount of linear bonds and the average amount of terminal groups, multiplied by 100, is 10 to 99.9%, preferably 20 to 20 99%, particularly preferably from 20 to 95%.

By "dendrimeric" it is understood, in the context of the present invention, that the degree of branching is 99.9%. For the definition of the "degree of branching" see H. Frey et al., Acta Polym. 1997, 48, 30.

It represents an important characteristic of polyesters that are not crosslinked. "Uncrosslinked" within the framework of this document means that there is a degree of crosslinking of less than 15% by weight, preferably less than 10% by weight, determined through the insoluble part of the polymer.

The insoluble part of the polymer was determined by extraction for four hours with the same solvent used for gel permeation chromatography, that is, selected from the group consisting of

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tetrahydrofuran, dimethylacetamide and hexafluoroisopropanol, depending on which solvent the polymer is most soluble in, in a Soxhlet apparatus and, after drying the residue until proof of weight, weighing of the remaining residue.

The structuring reaction of this type of polyesters is carried out by reacting the carboxy group of the oligohydroxycarboxylic acid with one of the hydroxy groups. In an ideal structuring reaction by esterification of n molecules of a bifunctional oligohydroxycarboxylic acid in relation to hydroxy groups, this would lead to a hyperbranched polyester with (n + 1) hydroxy groups and exactly one carboxy group. However, this ideal structure is actually altered by etherification reactions of hydroxy groups and by intramolecular esterification (lactone formation).

The etherification reaction leads to fewer hydroxy groups being ideally contained in the product. The intramolecularly formed ether groups have no effect on the amount of carboxy groups per molecule. On the contrary, for each ether group formed intramolecularly another free carboxy function is formed in the hyperbranched polyester. However, this goes against the requirement, according to the objective, of monofunctional and uniformly structured products. Therefore, it is necessary to suppress or at least displace the etherification reaction.

The formation of lactone is carried out by intramolecular reaction of a carboxy group with a hydroxy group and leads, in addition to an irregular structure, to a reduction of the free carboxy groups in the product. This reaction decreases the average functionality of carboxy groups in the product. However, this goes against the requirement, according to the objective, of monofunctional and uniformly structured products. That is, it is necessary to suppress or at least displace the formation of lactone. Since lactone formation decreases the functionality of carboxy groups in the molecule, while intermolecular etherification increases it, lactone formation is easier to tolerate than a reaction that leads to an increase in carboxy functionality. However, preferably also the formation of lactone is as reduced as possible.

The weight average molar weight Mw (determined by gel permeation chromatography by using poly (methyl methacrylate) standards of the hyperbranched polyesters according to the invention is, most often, between 500 and 300,000, preferably from 600 to 200,000 g / mol, the average molar weight in number Mn, between 400 and 50,000, preferably between 500 and 30,000 g / mol.

Polydispersity, as a rule, is 1.1 to 30, preferably 1.2 to 20.

The highly functional, highly branched or hyperbranched polyesters according to the invention are liquid or solid at room temperature (23 ° C) and, as a rule, have a glass transition temperature of -50 to 120 ° C, preferably -40 to 100 ° C and, particularly preferably, from -30 to 80 ° C. Such highly functional, highly branched or hyperbranched polyesters that are structured from aromatic oligohydroxycarboxylic acids can have a glass transition temperature of up to 180 ° C.

The glass transition temperature Tg is determined by the DSC (differential scanning calorimetry) method according to ASTM 3418/82, the heating rate is preferably 10 ° C / min.

The OH number according to DIN 53240, part 2 of the hyperbranched polyesters, as a rule, is 1 to 800 mg KOH / g, preferably 50 to 800 mg KOH / g, particularly preferably 80 to 700 mg KOH / g

It is essential according to the invention that the hyperbranched polyesters according to the invention have an average functionality of carboxy functions (-COOH) of more than 0.8, particularly preferably more than 0.9 and, very particularly preferred, more than 0.95 and less than 1.05.

With the average functionality is meant the average amount of the corresponding functional groups per molecule.

Unwanted macromolecules with different content of carboxy groups can be checked particularly well by mass spectrometry methods such as, for example, by MALDI-TOF analysis. In this way they can be separated, by adding different types (for example, with a cation with the "cat" molar mass of the series of salts of Li *, Na * or K *) during sample preparation before MALDI-TOF measurement, the signals of macromolecules containing carboxy groups of the signal series of the remaining components without carboxy groups. The macromolecules with carboxy groups can show in addition to the usual signals with the mass (M + cat) + because of the proton-cation exchange for each carboxy group containing additional signals, which have an increased mass value in the mass of the cation reduced in a unit of mass (cat-1). Thus, for each macromolecule depending on the functionality of carboxy groups a typical mass spectrometry signal pattern with mass separation of (cat-1) results.

The following three examples have to clarify this state of the facts: in the case of monofunctional macromolecules in relation to the carboxy groups in the MALDI-TOF only the cationized molecule ion appears

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(M + cat) + as well as the increased signal produced by proton-cation exchange in (M + (cat -1) + cat) +. The macromolecules with two carboxy groups per molecule show, in addition to these two series of signals, additionally a third series that proceeds by the double proton-cation exchange and which has a mass increased by 2 * (cat -1): (M + 2 * (cat -1) + cat) +. On the contrary, macromolecules without carboxy groups would show only the main signal in (M + cat) +, since without a free carboxy group no proton-cation exchange is possible.

Another characteristic of hyperbranched polyesters according to the invention is that they have a reduced average functionality of the ether group -CH2-O-CH2-. This frequently amounts to less than 0.2, preferably less than 0.15, particularly less than 0.10, more particularly preferably less than 0.06 and especially less than 0.04. Such ether groups are produced by inter-or intramolecular reaction of hydroxymethyl groups of oligohydroxycarboxylic acid units with each other. This has, in particular, the consequence that an irregular carboxy group is formed for each intermolecular ether group.

The content of ether groups -CH2-O-CH2-in the product can be determined by 13C NMR spectroscopy at 100 MHz in d6-DMSO. Thus, the CH2 groups of the -CH2-O-CH2-ether groups in the 13C NMR compared to the CH2 groups of the -CH2-O-OC-ester groups are deep-field displaced. For example, the CH2 groups of the ether groups in the hyperbranched polyester of dimethylolbutyric acid appear in a field approximately 2-10 ppm deeper than the CH2 groups of the ester groups appearing at approximately 58-63 ppm.

Another characteristic of hyperbranched polyesters according to the invention is that they have a reduced functionality of lactone groups. This, as a general rule, amounts to less than 0.10, preferably to less than 0.08, particularly preferably to less than 0.06, very particularly preferably to less than 0.04 and especially less than 0 , 02. Lactones are produced by intramolecular reaction of hydroxymethyl groups with carboxy groups already esterified or free. The reaction with free carboxy groups has, in particular, the consequence that a regular carboxy group is structured for each lactone. If, for example, two units of oligohydroxycarboxylic acid react with each other, then a dimeric ring system without carboxy groups is formed from this. In the reaction of correspondingly larger polyesters, macrocyclic lactones are formed without carboxy groups.

The content of lactones in the product can be determined, for example, by two-dimensional NMR spectroscopy by transanular interactions of hydrogen atoms.

The cyclic components of the hyperbranched polymer can also be checked particularly well by mass spectrometry methods such as, for example, by MALDI-TOF analysis. Thus, hyperbranched polymers containing one cycle per molecule, that is, an intramolecular ether linkage or an intramolecular ester linkage (lactone), have a shifted signal compared to the main signal 18 mass units towards lower mass values, since, in comparison to the main signal without cycle, they are produced by cleavage of an additional water molecule by macromolecule. Consequently, macromolecules with n cycles per molecule show a signal that is shifted, compared to the main signal, n * 18 mass units towards lower mass values.

The oligohydroxycarboxylic acids have, in addition to exactly one carboxy function, at least two hydroxy functions, for example, from two to five, preferably from two to four, particularly preferably from two to three and very particularly preferably exactly two.

The oligohydroxycarboxylic acids may contain aromatic groups or be aliphatic, preferably they are aliphatic.

The hydroxy groups may preferably be present in the form of hydroxymethyl groups (-CH2-OH).

An example of compounds with exactly one carboxy group presenting, in position 2 with respect to the carboxy group, more than two hydroxymethyl groups, is 2,2,2-tris (hydroxymethyl) acetic acid. One such oligohydroxycarboxylic acid containing hydroxy groups in a form other than hydroxymethyl groups is, for example, 2,3-dihydroxypropionic acid. Examples of compounds with exactly one carboxy group having more than two hydroxy groups have sugar acids such as gluconic acid, glucaric acid, glucuronic acid, galacturonic acid or mucic acid (galactic acid).

The use of aromatic dihydroxycarboxylic acids, such as 2,4-, 2,6-and, preferably, 3,5-dihydroxybenzoic acid or 4,4-bis (4-hydroxyphenyl) valeric acid, is conceivable and preferred.

Particularly preferred oligohydroxycarboxylic acids are 2,2-bis (hydroxymethyl) alkanocarboxylic acids.

2,2-bis (hydroxymethyl) alkanocarboxylic acids which can be used in accordance with the invention are, for example, those with five to twelve carbon atoms, preferably five to seven, particularly preferably six carbon atoms, such as , for example, 2,2-bis (hydroxymethyl) propionic acid (dimethylolpropionic acid), 2,2-bis (hydroxymethyl) butyric acid (dimethylolbutyric acid) and 2,2-bis (hydroxymethyl) valeric acid,

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preferably 2,2-bis (hydroxymethyl) propionic acid (dimethylolpropionic acid) or 2,2-bis (hydroxymethyl) butyric acid (dimethylolbutyric acid) and, particularly preferably, 2,2-bis (hydroxymethyl) butyric acid (dimethylolbutyric acid ).

Oligohydroxycarboxylic acids can be used as salts, for example, as ammonium or alkali metal salts or, preferably, as free acids.

In a preferred embodiment, the conversion according to the invention is carried out in the presence of no more than 25 mol% (in relation to the amount of oligohydroxycarboxylic acid), preferably no more than 10 mol%, of particularly preferably not more than 5 mol% and, very particularly preferably, in the absence of oligohydroxycarboxylic acid esters other than those esters of oligohydroxycarboxylic acid itself. In particular, the presence of oligohydroxycarboxylic acid esters that carry radical polymerizable groups is excluded. This would have the disadvantage that polymerization groups by polymerization sensitive radicals would be exposed during the esterification reaction to the esterification reaction conditions.

In another preferred embodiment, the conversion according to the invention is carried out in the absence of oligohydroxycarboxylic acid derivatives, in which the hydroxy groups are provided with the protective groups known to the expert, in particular they are carried out in absence of 1,3-dioxan-5-carboxylic acids substituted with 5-alkyl. In the case of these, they are products of conversion of oligohydroxycarboxylic acid with aldehydes or ketones, for example, acetonides.

In this regard, these 1,3-dioxan-5-carboxylic acids substituted with 5-alkyl may be mono-, di- or unsubstituted in position 2, being in the case of the alkyl group in position 5, preferably, a methyl or, particularly preferably, of an ethyl group.

Other protected derivatives of oligohydroxycarboxylic acids, in whose absence the reaction according to the invention is preferably carried out, are conversion products of oligohydroxycarboxylic acid in which hydroxy groups are linked through carbonate units or are protected with groups silyl

In another preferred embodiment, the conversion according to the invention is carried out in the absence of compounds containing exclusively hydroxy groups. Such compounds containing exclusively hydroxy groups are, for example, mono-, di- or polyalcohols, but also their esters an oligohydroxycarboxylic acids. It is disadvantageous in the case of the presence of such alcohols that these compounds can react with the carboxy groups and, therefore, would decrease the desired content according to the invention of the carboxy group.

For the preparation of the hyperbranched polyesters according to the invention it is decisive not to select the temperature during the reaction too high, since the etherification reaction and / or the formation of lactone is therefore favored.

As a general rule, the temperature during the reaction should not rise to more than 120 ° C, preferably not more than 110 ° C, particularly not more than 100 ° C and, more particularly preferably, no more than 90 ° C.

Obviously a minimum temperature is necessary to allow the reaction to develop at a reasonable speed. As a general rule, the temperature during the reaction should be at least 50 ° C, preferably at least 60 ° C and, particularly preferably, at least 70 ° C.

On the contrary, the duration of the reaction, as a general rule, has a lower order influence and also depends on the selected temperature. The higher the temperature, the shorter the reaction duration must be selected. The duration of the reaction should not exceed 48 hours, preferably not more than 36 hours, particularly preferably not more than 24 hours. However, as a general rule at least 2 hours are required, preferably at least 4 hours, particularly preferably at least 6 hours, very particularly preferably at least 8 hours and especially at least 12 hours.

It is decisive that a sufficient conversion of oligohydroxycarboxylic acid is guaranteed in the reaction. The conversion in relation to the reactive carboxy groups should amount to at least 50%, preferably at least 66%, particularly preferably at least 75%, very particularly preferably at least 80%, in particular at less than 85%, especially at least 90% and even at least 95%. Even greater conversions such as at least 97%, 98% or even 99% may also be reasonable.

The conversion can be followed, for example, by following the formation of the water released during the esterification reaction which, for example, can be removed by distillation, preferably removed by distillation azeotropically. However, it is also conceivable to bring the conversion to a significant increase in the viscosity of the reaction mixture.

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For this, the reaction is carried out in at least one, preferably exactly in a solvent. The solvent should preferably be inert under the reaction conditions, that is, not to react with the reactant, the intermediates or the product. A solvent is considered inert when under the reaction conditions it does not degrade by more than 5% by weight, in relation to the starting amount, in a discretionary manner, for example, by reaction with the reactant, intermediate or product or by decomposition thermal, preferably not more than 3, particularly preferably not more than 2, very particularly preferably not more than 1, in particular not more than 0.5 and in particular not more than 0.2% by weight .

As a consequence of this, the use of alcohols or compounds containing carbonyl groups as a solvent is less preferred. They are alcohols, for example, alkanols having 1 to 12 carbon atoms, optionally substituted, such as, for example, methanol, ethanol, iso-propanol, n-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol, cyclopentanol or cyclohexanol. They are compounds containing carbonyl groups, for example, aldehydes or in particular ketones, for example acetone, ethylmethyl ketone, diethyl ketone, isobutylmethyl ketone, cyclopentanone or cyclohexanone.

It is conceivable, although less preferred, the use of carboxylic acid esters as a solvent, for example, n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2 and 2-methoxyethyl acetate.

The solvent used must have sufficient solubility for oligohydroxycarboxylic acid. For this, those solvents that are sufficiently polar and have a relative dielectric constant of 5 to 80, preferably 7 to 50 and, particularly preferably, 7.4 to 40, are preferred.

Examples of this are halogenated hydrocarbons, preferably chlorinated hydrocarbons, for example, chlorinated aromatic or aliphatic compounds. Chlorobenzene, chlorotoluene, o-dichlorobenzene, methylene chloride, chloroform, 1,2-dichloroethane, 1,1-dichloroethane or 1,1,1-trichloroethane are preferred.

However, cyclic or acyclic ethers are also conceivable, for example, tetrahydrofuran, dioxanes, tert-butyl methyl ether or tert-butylethyl ether.

In principle, no limits are set above the boiling point of the solvent.

To enable separation by simple distillation of the solvent used after the end of the reaction, it is preferred to use those solvents with a boiling point at normal pressure of no more than 150 ° C.

In addition, it may be advantageous to use solvents with a boiling point at normal pressure that is above or corresponds to the reaction temperature. In this case, the reaction can be carried out simply at atmospheric pressure or normal pressure and the solvent, after the end of the reaction, can simply be removed by distillation.

Of course, it is also conceivable to use solvents with a lower boiling point. In this case, the reaction would have to be carried out under increased pressure to achieve the minimum required temperature.

In addition, at least one catalyst is added to the reaction that accelerates the esterification reaction. Such catalysts are known per se to the expert.

The catalyst is selected from the group consisting of acids, metal chelates, metal alcoholates, metal alkanoates and organometallic compounds.

Preferred acids are those with a pK value of less than 4.75, particularly preferably less than 4.0 and, in particular, less than 3.0.

As the acid esterification catalyst, para-toluenesulfonic acid is preferably used. Other useful acid esterification catalysts are organic sulfonic acids, for example methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, camphorsulfonic acid, cyclododecansulfonic acid and / or sulfuric acid. Corresponding mixtures can also be used. The content of the esterification catalyst, in relation to the reaction mixture contained therein, is appropriately 0.1 to 10% by weight, preferably 0.1 to 6% by weight. In principle, carboxylic acids are also conceivable as a catalyst, provided they have a sufficient acid strength. But since carboxylic acids themselves are reactive and, therefore, can also react further, carboxylic acids are less preferred catalysts.

The metal compounds are alkanolates, alkanoates, chelates or organometallic compounds of the metals of groups IIIA to VIIIA or IB to VB in the periodic system of the elements.

Preferred metals are boron, aluminum, tin, zinc, titanium, antimony, zirconium or bismuth.

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In this respect, cyclic compound chelates in which metals and clusters with pairs of electrons alone form a ring. A preferred chelate former is acetyl acetone. An example of such a catalyst is zirconium acetyl acetone.

Alkanolates are, for example, C1-C10 alkanolates, preferably C1-C4 alkanolates, methanolate, ethanolate, iso-propanolate and n-butanolate are particularly preferred, methanolate and ethanolate are particularly preferred and in particular methanolate.

Alkanoates are, for example, C1-C20 alkanoates, C1-C4 alkanoates are preferred, acetate is particularly preferred.

Organometallic compounds are those with a direct metal-carbon bond.

Preferred metal compounds as catalysts are titanium tetrabutanolate, titanium tetraisopropanolate, zirconium tetrabutanolate, tin n-octanoate (II), tin 2-ethylhexanoate (II), tin laurate (II), dibutyltin oxide, dichloride of dibutyltin, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin diacetate, antimony triethanolate or boronic acid derivatives, for example, pyridinoboronic acid.

The modification of the hyperbranched polyesters according to the invention with monofunctional acids, for example, carboxylic acids or sulphonic acids, preferably carboxylic acids, may represent a preferred embodiment. This modification can be performed after the completion of the conversion of oligohydroxycarboxylic acid or, preferably, during the conversion of oligohydroxycarboxylic acid.

In addition, mixtures of two or more of the acids mentioned above may be used. Acids can be used as such or in the form of derivatives. Such derivatives are in particular

- the anhydrides of the mentioned acids and, in fact, in monomeric or even polymeric form;

- esters of the acids mentioned, for example

•

mono- or dialkyl esters, preferably C1 to C4 alkyl esters, particularly preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, but also mono- and dialkyl esters derived from higher alcohols such as , for example, n-propanol, iso-propanol, nbutanol, isobutanol, tert-butanol, n-pentanol, n-hexanol,

•

mono-and divinyl esters as well as

•

mixed esters, preferably methyl ethyl ester.

For example, hyperbranched polymers can be reacted with alkyl or alkenylcarboxylic acids such as, for example, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, hexadecanoic acid, stearic acid, oleic acid, linoleic acid, linolenic acid or their salts of Li, Na, K, Cs, Ca or ammonium, with alkylsulfonic acids, for example, octansulfonic acid, dodecansulfonic acid, stearylsulfonic acid or oleylsulfonic acid or their salts of Li, Na, K, Cs, Ca or ammonium, with acid camphor sulfonic acid, cyclododecylsulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, 4-hexylbenzene sulfonate, 4octylbenzene sulfonate, 4-decylbenzene sulfonate or 4-dodecylbenzene sulfonate or its salts of Li, Na, K, Cs, Ca or ammonium, with alkyl sulfates, for example, with n-alkyl sulfates or with secondary alkyl sulfates.

The alkyl, alkenyl, cycloalkyl or aryl moieties in this regard may have up to 20 carbon atoms, preferably from 6 to 20, particularly preferably from 7 to 20.

However, conversion with acids containing oxyalkylene groups is also conceivable. In this respect, it is preferably those acids of formula

R2 - [- CH2-CH2-O] and-R3-COOH

in which

R2 is an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms,

and is equal to 0 or a positive integer from 1 to 20 and

R3 is an alkylene group having from 1 to 8, preferably from 1 to 4, particularly preferably from 1 to 2 and, very particularly preferably, a carbon atom.

In this regard, an alkyl group having 1 to 8 carbon atoms means methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-hexyl , n-heptyl, n-octyl and 2-ethylhexyl.

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By an alkylene group having 1 to 8 carbon atoms is methylene, 1,1-ethylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene , 1,4-butylene and 1,6-hexylene.

Preferably, in the case of R2 it is methyl, ethyl or n-butyl, preferably methyl or n-butyl and, particularly preferably, methyl.

Preferably, and is a number from 1 to 10, particularly preferably from 1 to 5 and, very particularly preferably, 1, 2 or 3.

Preferably, R3 is methylene or 1,2-ethylene, particularly preferably methylene.

Of the mentioned monofunctional acids, 0 to 40 mol%, preferably 0 to 30 mol%, particularly preferably 0 to 20 mol%, very particularly preferably 0 to 10 mol% can be reacted and especially 0 mol% in relation to the oligohydroxycarboxylic acid employed.

It may be another preferred embodiment to modify the hyperbranched polyesters according to the invention with monohydroxycarboxylic acids or their derivatives. This modification can be performed after the completion of the conversion of oligohydroxycarboxylic acid or, preferably, during the conversion of oligohydroxycarboxylic acid.

In this respect they are derivatives as defined above and may be, additionally and preferably, lactones.

Examples of lactones in this regard are gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, gammacaprolactone and epsilon-caprolactone.

Examples of monohydroxycarboxylic acids are those of formula

4

HO-R-COOH

in which

R4 is an alkylene group having from 1 to 8, preferably from 2 to 6, particularly preferably from 3 to 5 and, very particularly preferably, from 3 or 4 carbon atoms.

Preferably, in the case of R4, it is a unit of α, ω-alkylene, although units of α, (ω-1) -o α, (ω-2) -alkylene are conceivable, although less preferred.

Of the aforementioned monohydroxycarboxylic acids, 0 to 40 mol%, preferably 0 to 30 mol%, particularly preferably 0 to 20 mol%, very particularly preferably 0 to 10 mol% can be reacted and especially 0 mol% in relation to the oligohydroxycarboxylic acid employed.

The hyperbranched, monofunctional polyesters in relation to the carboxylic acid group, prepared in accordance with the invention are thus preferably reacted to those hyperbranched polyesters in which the carboxy function is derivatized with exactly a radical polymerizable group.

They are radical polymerizable groups, for example, allyl groups, vinyl ether groups and preferably acrylate and methacrylate groups, the latter being briefly summarized herein as (meth) acrylate groups, as well as conjugated double bonds to aromatic systems.

Allyl groups (H2C = CH-CH2-) may be present as such or, preferably, as allyl ether groups (H2C = CH-CH2-O-), however allyl ester groups (H2C = are also conceivable) CH-CH2-O-CO-).

Vinyl ether groups (H2C = CH-O-) may also be present as an alternative also as vinyl ester groups (H2C = CH-O-CO-).

Conjugated double bonds to aromatic systems are, for example, those such as are present in styrene, α-methylstyrene, cinnamic acid or cinnamic acid esters.

Derivatization is carried out by reacting the carboxy group of the hyperbranched polyesters with at least one compound that carries at least one, preferably exactly one reactive group against carboxy groups and exactly one radical polymerizable group, preferably a (meth) acrylate group.

Such compounds are preferably those of formula

[RG] x-R1-Acr

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in which

it refers to a positive integer of at least 1, preferably 1 to 3, particularly preferably 1 to 2 and, very particularly preferably, with accuracy 1,

RG to a reactive group against carboxy groups,

R1 to an organic residue of Valencia (x + 1) that has 1 to 20 carbon atoms and

Acr to a radical polymerizable group.

In this regard, R1 may preferably represent C6-C12 arylene, C3-C12 cycloalkylene, C1-C20 alkylene or C2-C20 alkylene interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted imino groups or unsubstituted and / or one or more groups - (CO) -, -O (CO) O-, - (NH) (CO) O-, -O (CO) (NH) -, -O (CO) - or - (CO) O-.

In the same they mean C3-C12 cycloalkylene, for example, cyclopropylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclododecylene, C6-C12 arylene, for example, 1,2-, 1,3-or 1,4-phenylene, 2,3- , 2,4-, 2,5-or 2,6-toluylene, 1,8-, 1,5-or 2,6-naphthylene and C1-C20 alkylene, linear or branched alkylene, for example, methylene, 1,2- ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 1,1-dimethyl-1,2-ethylene or 1,2-dimethyl-1,2 -ethylene, 1,6-hexylene, 1,8-octylene or 1,10-decylene.

The amount of oxygen and / or sulfur atoms and / or imino groups in the C2-C20 alkylene is not limited. As a general rule, it does not amount to more than 5 in the rest, preferably not more than 4 and, more particularly preferably, not more than 3.

In addition, between two heteroatoms, as a rule, there is at least one carbon atom, preferably at least two.

The substituted and unsubstituted imino groups can be, for example, imino, methylimino, iso-propylimino, n-butylimino

or tert-butylimino.

Examples of such interrupted C2-C20 alkylenes are 1-oxa-1,3-propylene, 1,4-dioxa-1,6-hexylene, 1,4,7-trioxa-1,9nonylene, 1-oxa-1,4 -butylene, 1,5-dioxa-1,8-octylene, 1-oxa-1,5-pentylene, 1-oxa-1,7-heptylene, 1,6-dioxa-1,10decylene, 1-oxa-3 -methyl-1,3-propylene, 1-oxa-3-methyl-1,4-butylene, 1-oxa-3,3-dimethyl-1,4-butylene, 1-oxa-3,3-dimethyl-1 , 5pentylene, 1,4-dioxa-3,6-dimethyl-1,6-hexylene, 1-oxa-2-methyl-1,3-propylene, 1,4-dioxa-2,5-dimethyl-1,6 -hexylene, 1-oxa1,5-pent-3-enylene, 1-oxa-1,5-pent-3-inylene, 1,1-, 1,2-, 1,3-or 1,4-cyclohexylene, 1,2-or 1,3-cyclopentylene, 1,2-, 1,3-or 1,4-phenylene, 4,4'-biphenylene, 1,4-diaza-1,4-butylene, 1-aza- 1,3-propylene, 1,4,7-triaza-1,7-heptylene, 1,4-diaza-1,6hexylene, 1,4-diaza-7-oxa-1,7-heptylene, 4,7- diaza-1-oxa-1,7-heptylene, 4-aza-1-oxa-1,6-hexylene, 1-aza-4-oxa-1,4butylene, 1-aza-1,3-propylene, 4- aza-1-oxa-1,4-butylene, 4-aza-1,7-dioxa-1,7-heptylene, 4-aza-1-oxa-4-methyl-1,6hexylene, 4-aza-1, 7-dioxa-4-methyl-1,7-heptylene, 4-aza-1,7-dioxa-4- (2'-hydro xyethyl) -1,7-heptylene, 4-aza-1-oxa- (2'hydroxyethyl) -1,6-hexylene or 1,4-piperazinylene.

In this regard, R1 preferably refers to methylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,6hexylene, 1,8-octylene or 1,10-decylene .

Examples of radical polymerizable groups are Acr, allyl, metalyl, vinyl ether, acryl, methacryl, methacryl as well as 2-phenyl-ethene-1-yl (styrene) groups, preferably (meth) acrylate groups and, particularly preferably, acrylate groups.

Examples of reactive groups against RG carboxy groups are primary amino groups, secondary amino groups, aziridines, azetidinium compounds and preferably epoxy groups.

Preferably, in the case of these compounds, they are the formal conversion products of epichlorohydrin (1-chloro-2,3-epoxypropane) with a compound that contains exactly one radical polymerizable group and at least one, preferably one to three , particularly preferably one to two and, very particularly preferably, exactly an acid function.

Such compounds that contain exactly one radical polymerizable group and at least one acid function are, for example, acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, vinyl sulfonic acid, vinyl phosphonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, 2-or 3-sulfopropyl acrylate, 2-or 3-sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropyl , 2-hydroxy-3-methacryloxypropylsulfonic acid, allylphosphonic acid, styrenesulfonic acid, cinnamic acid, 2-acrylamido-2-methylpropanesulfonic acid or 2-acrylamido-2-methylpropanophosphonic acid, as well as their amides, hydroxyalkyl esters and esters and amides containing amino or ammonium groups and in multiple acids partially esterified compounds having At least one carboxy group was present.

Acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, vinyl sulfonic acid and acid are preferred.

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cinnamic, acrylic acid, methacrylic acid, crotonic acid, malic acid and fumaric acid are particularly preferred, acrylic acid and methacrylic acid, in particular acrylic acid, are particularly preferred.

Examples of compounds having at least one and exactly one radical polymerizable group are allyl glycidyl ether, vinyl glycidyl ether, glycidyl acrylate and glycidyl methacrylate, glycidyl acrylate and glycidyl methacrylate are preferred.

The conversion of the carboxy group of the hyperbranched polyester with the compound having at least one reactive group against carboxy groups and exactly one radical polymerizable group is carried out, for example, under the following reaction conditions:

the stoichiometry of the reaction is, for example, from 0.75 to 1.25, preferably from 0.8 to 1.2, particularly preferably from 0.9 to 1.1 and, very particularly preferably, from 0.95 to 1.05 moles of reactive groups against carboxy groups per mole of carboxy groups in the hyperbranched polyester (for example, determinable through their acid number).

For the reaction, both components or, preferably, the hyperbranched polyester can optionally be dissolved in a solvent. In this regard, the same solvents described above for the esterification reaction of oligohydroxycarboxylic acids can be treated. However, alcohols and solvents containing carbonyl groups are likewise preferred here.

The solvent used must have sufficient solubility for the reaction components. For this purpose, for example, those solvents that are sufficiently polar and have a relative dielectric constant of 5 to 80, preferably 7 to 50 and, particularly preferably, 7.4 to 40, are preferred.

Polar aprotic solvents are preferred, dimethylformamide, dimethylacetamide, acetonitrile and dimethylsulfoxide are particularly preferred.

Most of the time the hyperbranched polyester, dissolved in a solvent, is disposed and the compound having at least one reactive group against carboxy groups and exactly one radical polymerizable group is added in portions.

The reaction temperature may be 50 to 120 ° C, preferably 60 to 100 ° C, particularly preferably 70 to 90 ° C.

The duration of the reaction depends on the selected temperature. As a general rule, 24 hours are sufficient, preferably less than 18 hours and, particularly preferably, less than 14 hours. However, as a general rule at least one hour is required, preferably at least 2 hours, particularly preferably at least 4 hours, very particularly preferably at least 6 hours and especially at least 10 hours.

To accelerate the reaction it may be advantageous to add at least one catalyst. Examples of this are amines, tertiary amines are preferred. Particularly preferred is tributylamine.

The use of highly functional, highly branched, hyperbranched polyesters according to the invention that carry a polymerizable group as a monomer or comonomer in radical polymerization is also an object of the present invention. Polymers or copolymers obtained from such (co) polymerization are suitable, for example, in lacquer systems, in particular in the so-called double cure lacquer system in which curing is carried out through different mechanisms. of curing, here for example by radical curing of the radical polymerizable group and by reaction of the hydroxy groups with polyisocyanates.

Examples

Example 1 conversion of dimethylolbutyl acid into 1,2-dichloroethane, catalyzed with para-toluenesulfonic acid

In a 4 l three-neck flask, equipped with water separator, internal thermometer and stirrer, 250 g of dimethylolbutyric acid (DMBA) were mixed with 1.4 l of 1,2-dichloroethane and 5.0 g of acid were added paratoluenesulfónico as catalyst. The reaction mixture was then heated to reflux (approximately 83 ° C) and the water produced during esterification was separated through the water separator. After 19 h of reaction time, 24.6 g of water were removed in total, which corresponds to a conversion of approximately 83%. The polymeric product is deposited in the course of the reaction in the form of a white solid in the wall of the flask. The 1,2-dichloroethane solvent is then removed by filtration or distillation.

The average molar weight in Mn number of the represented polyester was determined by GPC (eluent: hexafluoroisopropanol [HFIP], calibration: PMMA (poly (methyl methacrylate)) at 1,100 g / mol, the average molar weight by weight Mw at 2,200 g / mol The acid number was determined according to DIN 53240, part 2, in 43 mg KOH / g polymer.

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Example 1 a

Within a test example analogous to Example 1, a total of 20.5 g of water was removed, which corresponds to a lower conversion of approximately 67%. In this case, the polymer product was also deposited in the course of the reaction in the form of a white solid on the wall of the flask. The solvent 1,2-dichloroethane was then removed by filtration or distillation.

The average molar weight in number Mn of the represented polyester was determined by GPC (eluent: hexafluoroisopropanol [HFIP], calibration: PMMA) at 1,100 g / mol, the average molar weight by weight Mw in

1,700 g / mol.

Example 2 (comparison with Example 1): conversion of dimethylolbutyric acid to dichloromethane, catalyzed with para-toluenesulfonic acid

In a 4 l three-neck flask, equipped with water separator, internal thermometer and stirrer, 250 g of dimethylolbutyric acid (DMBA) were mixed with 1.4 l of dichloromethane and 5.0 g of paratoluenesulfonic acid were added as catalyst. The reaction mixture was then heated to reflux (approximately 40 ° C) and the water produced during esterification was removed through the water separator. In this case it is shown that the reaction rate at 40 ° C is too low for the water to be significantly removed from the reaction preparation.

Example 3 (comparison with Example 1): conversion of dimethylolbutyric acid into 1,1,2,2-tetrachloromethane, catalyzed with para-toluenesulfonic acid

100 g of dimethylolbutyric acid (DMBA) with 1.4 l of 1,1,2,2-tetrachloroethane were mixed in a 4-l flask, equipped with a water separator, internal thermometer and stirrer, and 2 were added, 0 g paratoluenesulfonic acid as catalyst. The reaction mixture was then heated to reflux (approximately 147 ° C) and the water produced during esterification was removed through the water separator. After 12 h of reaction time, a total of 26.3 g of water was removed, which corresponds to a conversion of approximately 88%. The solvent 1,1,2,2-tetrachloroethane was then removed by distillation. The product contains clear parts of components with more than one COOH group per molecule.

Example 4 (comparison with Example 1): conversion of dimethylolbutyric acid into acetone, catalyzed with titanium butylate (IV)

In a flask of three mouths of 4 l, equipped with distillation compound composed of a descending refrigerator and a disposal flask, internal thermometer and stirrer, 151 g of dimethylolbutyric acid (DMBA) were mixed with 0.2 g of titanium butylate ( IV) as a catalyst, they were dissolved in acetone without water and slowly heated. In this regard, acetone was continuously removed from the reaction mixture by distillation, which serves as a entrainment agent for the secondary water condensation product. To compensate for the loss of solvent that appears in this case, new acetone without water was added in parallel to this in an amount corresponding to the mixture. The progress of the reaction was followed by determination of the water content in the individual acetone distillates by Karl-Fischer titration. After approximately 72 hours of reaction time approximately 15.6 g of water were removed in total, which corresponds to a conversion of approximately 85%. The product contains mostly components with diol units protected with acetonide which, in another reaction stage, have yet to be cleaved again, which would mean unnecessary additional complexity.

Example 5 (comparison with Example 1): conversion of dimethylolbutyric acid without solvent, catalyzed with para-toluenesulfonic acid

In a flask of three mouths of 4 l, equipped with distillation wall composed of a short Vigreux column, a descending refrigerator and a flask of disposal, internal thermometer and stirrer, 100 g of dimethylolbutyric acid (DMBA) were mixed with 2.0 g of para-toluenesulfonic acid as catalyst and slowly heated. In this regard, the reaction mixture was heated to 220 ° C and water produced during esterification was removed through the distillation apparatus. After approximately 3 h of reaction time, a total of 10.1 g of water was removed, which corresponds to a conversion of approximately 82%. The product contains clear parts of components with more than one COOH group per molecule.

Example 6 (comparison with Example 1): conversion of dimethylolbutyric acid without solvent, catalyzed with titanium butylate (IV)

In a flask of three mouths of 4 l, equipped with distillation wall composed of a short Vigreux column, a descending refrigerator and a flask of disposal, internal thermometer and stirrer, 100 g of dimethylolbutyric acid (DMBA) were mixed with 2.0 g of titanium butylate (IV) as catalyst and slowly heated. In this regard, the reaction mixture was heated to 220 ° C and water produced during esterification was removed through the distillation apparatus. After 1.5 h of reaction time, a total of 10.2 g of water was removed, which

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which corresponds to a conversion of approximately 83%. The product contains clear parts of components with more than one COOH group per molecule.

Example 7: conversion of dimethylolbutyric acid and dimethylolpropionic acid into 1,2-dichloroethane, catalyzed with para-toluenesulfonic acid

In a 4 l three-neck flask, equipped with water separator, internal thermometer and stirrer, 132 g of dimethylolbutyric acid (DMBA) and 118 g of dimethylolpropionic acid (DMPA) were mixed with 2.0 l of 1,2-dichloroethane and 5.0 g of para-toluenesulfonic acid was added as catalyst. The reaction mixture was then heated to reflux (approximately 84 ° C) and the water produced during esterification was removed through the water separator. After 20 h of reaction time, a total of 27.5 g of water was removed, which corresponds to a conversion of approximately 90%. The polymeric product was deposited in the course of the reaction as a white solid on the wall of the flask. The solvent 1,2-dichloroethane was then removed by filtration or distillation.

The average molar weight in number Mn of the represented polyester was determined by GPC (eluent: hexafluoroisopropanol [HFIP], calibration: PMMA) at 2,200 g / mol, the average molar weight by weight Mw in

4,200 g / mol. The acid number was determined according to DIN 53240, part 2, in 24 mg KOH / g polymer.

Example 8: conversion of dimethylolpropionic acid into 1,2-dichloroethane, catalyzed with para-toluenesulfonic acid

In a 4 l three-neck flask, equipped with water separator, internal thermometer and stirrer, 250 g of dimethylolpropionic acid (DMPA) were mixed with 2.0 l of 1,2-dichloroethane and 5.0 g of acid were added paratoluenesulfónico as catalyst. The reaction mixture was then heated to reflux (approximately 84 ° C) and the water produced during esterification was removed through the water separator. After 36 h of reaction time, a total of 32.0 g of water was removed, which corresponds to a conversion of approximately 96%. The polymeric product was deposited in the course of the reaction as a white solid on the wall of the flask. The solvent 1,2-dichloroethane was then removed by filtration or distillation.

The average molar weight in number Mn of the represented polyester was determined by GPC (eluent: hexafluoroisopropanol [HFIP], calibration: PMMA) at 5,400 g / mol, the average molar weight by weight Mw in

15,400 g / mol. The acid number was determined according to DIN 53240, part 2, in 10 mg KOH / g polymer.

Example 9: conversion of dimethylolbutyric acid and isononanoic acid into 1,2-dichloroethane, catalyzed with paratoluenesulfonic acid

In a 4 l three-neck flask, equipped with water separator, internal thermometer and stirrer, 236 g of dimethylolbutyric acid (DMBA) and 24.5 g of isononanoic acid were mixed with 2.0 l of 1,2-dichloroethane and 5.0 g of para-toluenesulfonic acid was added as catalyst. The reaction mixture was then heated to reflux (approximately 85 ° C) and the water produced during esterification was removed through the water separator. After 48 h of reaction time, a total of 18.4 g of water were removed, which corresponds to a conversion of approximately 60%. The 1,2-dichlorethane solvent was then removed by filtration

or distillation

Example 10: conversion of dimethylolbutyric acid and isononanoic acid into 1,2-dichloroethane, catalyzed with para-toluenesulfonic acid

In a 4 l three-neck flask, equipped with water separator, internal thermometer and stirrer, 236 g of dimethylolbutyric acid (DMBA) and 49.0 g of isononanoic acid were mixed with 2.0 l of 1,2-dichloroethane and 5.0 g of para-toluenesulfonic acid was added as catalyst. The reaction mixture was then heated to reflux (approximately 84 ° C) and the water produced during esterification was removed through the water separator. After 24 h of reaction time, a total of 21.0 g of water was removed, which corresponds to a conversion of approximately 63%. The 1,2-dichlorethane solvent was then removed by filtration

or distillation

Example 11: Conversion of dimethylolbutyric acid and γ-butyrolactone into 1,2-dichloroethane, catalyzed with paratoluenesulfonic acid

In a 4 l three-neck flask, equipped with water separator, internal thermometer and stirrer, 236 g of dimethylolbutyric acid (DMBA) and 13.5 g of γ-butyrolactone were mixed with 2.0 l of 1,2-dichloroethane and 5.0 g of para-toluenesulfonic acid was added as catalyst. The reaction mixture was then heated to reflux (approximately 84 ° C) and the water produced during esterification was removed through the water separator. After 48 h of reaction time, a total of 17.5 g of water were removed, which corresponds to a conversion of approximately 63%. The 1,2-dichlorethane solvent was then removed by filtration

or distillation

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Example 12: conversion of dimethylolbutyric acid and 2- [2- (2-methoxyethoxy) -ethoxy] acetic acid into 1,2-dichloroethane, catalyzed with para-toluenesulfonic acid

In a 4 l three-neck flask, equipped with water separator, internal thermometer and stirrer, 756 g of dimethylolbutyric acid (DMBA) and 198 g of 2- [2- (2-methoxyethoxy) -ethoxy] acetic acid were mixed with 2.0 L of 1,2-dichloroethane and 5.0 g of para-toluenesulfonic acid were added as catalyst. The reaction mixture was then heated to reflux (approximately 84 ° C) and the water produced during esterification was removed through the water separator. After 25 h of reaction time, a total of 93.5 g of water were removed, which corresponds to a conversion of approximately 87%. The 1,2-dichloroethane solvent was then removed by filtration or distillation.

Example 13: Conversion of the polyester of Example 1 with glycidyl methacrylate

320 g of a solution of the polyester of Example 1 in dimethylformamide (DMF) (16% by weight) was dried with 50 g of molecular sieve and then placed in a three 1-mouth flask, equipped with stirrer, internal thermometer and reflux refrigerator. Then, corresponding to the number of the acid groups in the polyester, 14.8 g of glycidyl methacrylate (1 equivalent in relation to the number of COOH groups), the tributylamine catalyst (0.97 g) was added as well as the hydroquinone monomethyl ether stabilizers (MEHQ, 0.03 g) and 2,6-diterc-butyl-4-methylphenol (DBPC, 0.03 g). The mixture was stirred for 12 h at 80 ° C. After this the solvent in the rotary evaporator was removed.

The average molar weight in number Mn of the represented polyester containing a polymerizable group was determined by GPC (eluent: hexafluoroisopropanol [HFIP], calibration: PMMA) at 1,100 g / mol, the average molecular weight by weight Mw at 5,000 g / mol. The acid number was determined according to DIN 53240, part 2, in 0.1 mg KOH / g polymer.

Example 14: Conversion of the polyester of Example 7 with glycidyl methacrylate

325 g of a solution of the polyester of Example 7 in dimethylformamide (DMF) (10% by weight) was dried with 80 g of molecular sieve and then placed in a three-mouth flask of 1 l, equipped with stirrer, internal thermometer and reflux refrigerator. Then, 2.2 g of glycidyl methacrylate (1.1 equivalents in relation to the number of COOH groups), the tributylamine catalyst (0.52 g) was added correspondingly to the number of the acid groups in the polyester ) as well as the hydroquinone monomethyl ether stabilizers (MEHQ, 0.02 g) and 2,6-diterc-butyl-4-methylphenol (DBPC, 0.02 g). The mixture was stirred for 16 h at 80 ° C. After this the solvent in the rotary evaporator was removed.

The average molar weight in number Mn of the represented polyester was determined by GPC (eluent: hexafluoroisopropanol [HFIP], calibration: PMMA) at 2,300 g / mol, the average molecular weight by weight Mw in

4,600 g / mol. The acid number was determined according to DIN 53240, part 2, in 0.1 mg KOH / g polymer.

Example 15: Conversion of the polyester of Example 8 with glycidyl methacrylate

113 g of a solution of the polyester of Example 8 in dimethylformamide (DMF) (10% by weight) was dried with 30 g of molecular sieve and then placed in a 1 l three-neck flask, equipped with stirrer, internal thermometer and reflux refrigerator. Then, corresponding to the number of acid groups in the polyester, 0.32 g of glycidyl methacrylate (1.1 equivalents relative to the number of COOH groups), the tributylamine catalyst (0.17 g) was added ) as well as the hydroquinone monomethyl ether stabilizers (MEHQ, 0.01 g) and 2,6di-tert-butyl-4-methylphenol (DBPC, 0.01 g). The mixture was stirred for 16 h at 80 ° C. After this the solvent in the rotary evaporator was removed.

The average molar weight in number Mn of the represented polyester was determined by GPC (eluent: hexafluoroisopropanol [HFIP], calibration: PMMA) at 5,000 g / mol, the average molecular weight by weight Mw in

17,700 g / mol. The acid number was determined according to DIN 53240, part 2, in 0.0 mg KOH / g polymer.

Claims (29)

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one.

Hyperbranched polyesters with a weight average molecular weight Mw of between 500 and 300,000 g / mol, obtainable by conversion of at least one oligohydroxycarboxylic acid in the presence of at least one catalyst and in the presence of at least one inert solvent under the reaction conditions, characterized in that the temperature during the reaction is adjusted to no more than 120 ° C, the average functionality of carboxy functions per molecule amounts to more than 0.8 and less than 1.05 and the average functionality of ether groups -CH2-O- CH2-amounts to less than 0.20 and the catalyst is selected from the group consisting of acids, metal chelates, metal alcoholates, metal alkanoates and organometallic compounds.

2.

Hyperbranched polyesters according to claim 1, characterized in that additionally the average functionality in lactones amounts to less than 0.10.

3.

Hyperbranched polyesters according to one of the preceding claims, characterized in that in the case of oligohydroxycarboxylic acid it is a dihydroxyalkanecarboxylic acid.

Four.

Hyperbranched polyesters according to one of claims 1 or 2, characterized in that in the case of oligohydroxycarboxylic acid it is a 2,2-bis (hydroxymethyl) alkanocarboxylic acid.

5.

Hyperbranched polyesters according to one of the preceding claims, characterized in that the conversion is carried out in the absence of oligohydroxycarboxylic acid esters other than those esters of oligohydroxycarboxylic acid with itself.

6.

Hyperbranched polyesters according to one of the preceding claims, characterized in that the conversion is carried out in the absence of 1,3-dioxan-5-carboxylic acids substituted with 5-alkyl.

7.

Hyperbranched polyesters according to one of the preceding claims, characterized in that the conversion is carried out in the absence of compounds containing exclusively hydroxy groups.

8.

Hyperbranched polyesters according to one of the preceding claims, characterized in that in the case of oligohydroxycarboxylic acid it is dimethylolpropionic acid.

9.

Hyperbranched polyesters according to one of claims 1 to 7, characterized in that in the case of oligohydroxycarboxylic acid it is dimethylolbutyric acid.

10.

Hyperbranched polyesters according to one of claims 1 to 7, characterized in that the oligohydroxycarboxylic acid is selected from the group consisting of 3,5-dihydroxybenzoic acid and 4,4-bis (4-hydroxyphenyl) valeric acid.

eleven.

Hyperbranched polyesters according to one of the preceding claims, characterized in that the solvent has a boiling point at normal pressure of no more than 150 ° C.

12.

Hyperbranched polyesters according to one of the preceding claims, characterized in that the solvent has a relative dielectric constant of 5 to 80.

13.

Hyperbranched polyesters according to one of the preceding claims, characterized in that in the case of the catalyst it is an acid with a pK value of less than 4.75.

14.

Hyperbranched polyesters according to one of claims 1 to 12, characterized in that in the case of the catalyst it is an organometallic compound.

fifteen.

Hyperbranched polyesters according to one of the preceding claims, characterized in that the conversion is carried out in the presence of monofunctional acids or their derivatives.

16.

Hyperbranched polyesters according to one of claims 1 to 14, characterized in that after conversion of the oligohydroxycarboxylic acid is completed, a conversion with monofunctional acids is carried out.

17.

Hyperbranched polyesters according to one of claims 15 or 16, characterized in that in the case of the monofunctional acid it is a carboxylic acid or a sulphonic acid.

18.

Hyperbranched polyesters according to one of claims 15 or 16, characterized in that in the case of monofunctional acid it is an alkyl-or alkenylcarboxylic acid, whose alkyl or alkenyl moiety has up to 20 carbon atoms.

19.

Hyperbranched polyesters according to one of claims 15 or 16, characterized in that the monofunctional acid has the formula

R2 - [- CH2-CH2-O] and-R3-COOH 14 5 10 fifteen twenty 25 30 35 40 Four. Five E08717828 09-30-2014 wherein R2 is an alkyl group having 1 to 8 carbon atoms, and is equal to 0 or a positive integer from 1 to 20 and R3 is an alkylene group having 1 to 8 carbon atoms.

twenty.

Hyperbranched polyesters according to one of the preceding claims, characterized in that the conversion is carried out in the presence of monohydroxycarboxylic acids or their derivatives.

twenty-one.

Hyperbranched polyesters according to claim 20, characterized in that the monohydroxycarboxylic acid is one of the formula

4 HO-R-COOH wherein R4 is an alkylene group having from 1 to 8, preferably from 1 to 4, particularly preferably from 1 to 2 and very particularly preferably a carbon atom.

22

Radically polymerizable hyperbranched polyesters, characterized in that hyperbranched polyesters are reacted according to one of the preceding claims with at least one compound that carries at least one reactive group against carboxy groups and exactly one radical polymerizable group.

2. 3.

Radically polymerizable hyperbranched polyesters according to claim 22, characterized in that the radical polymerizable group is selected from the group consisting of allyl, metalyl, vinyl ether, acryl, methacryl and 2-phenyl-ethe-1-yl groups (styrene ).

24.

Radically polymerizable hyperbranched polyesters according to claim 22, characterized in that in the case of the compound that carries at least one reactive group against carboxy groups and exactly one radical polymerizable group it is the formal conversion product of epichlorohydrin (1- chloro-2,3-epoxypropane) with a compound that contains exactly one radical polymerizable group and at least one acidic function.

25.

Radically polymerizable hyperbranched polyesters according to claim 24, characterized in that in the case of the compound that contains exactly one group that is polymerizable by radicals and at least one acid function, it is acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid , crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, vinyl sulfonic acid, vinyl phosphonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, 2-or 3-sulfopropyl acrylate , 2-or 3-sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, allylphosphonic acid, styrenesulfonic acid, cinnamic acid, 2-acrylamido-2-methylpropanesulfonic acid or 2-acrylamide -methylpropanophosphonic, as well as its amides, hydroxyalkyl esters and esters and amides qu e contain amino groups or ammonium groups and in multiple acids partially esterified compounds that still have at least one carboxy group.

26.

Radically polymerizable hyperbranched polyesters according to claim 22, characterized in that in the case of the compound bearing at least one reactive group against carboxy groups and exactly one radical polymerizable group, it is allyl glycidyl ether, vinyl glycidyl ether, glycidyl acrylate or glycidyl methacrylate.

27.

Process for the preparation of radical polymerizable hyperbranched polyesters according to one of claims 22 to 26, characterized in that at least one hyperbranched polyester according to one of claims 1 to 19 is reacted with at least one compound leading to the less a reactive group against carboxy groups and exactly a radical polymerizable group.

28.

Use of highly functional, highly branched, hyperbranched radical polymerizable polyesters according to one of claims 22 to 26 as a monomer or comonomer in radical polymerization.

29.

Use of polymers or copolymers obtained from a (co) polymerization, containing highly functional, highly branched, hyperbranched radical polymerizable polyesters according to one of claims 22 to 26 as monomer or comonomer in the form introduced by polymerization, in systems lacquer

fifteen